CN103346176A - Laminated solar cell based on different-grain-diameter PbS quantum dots and preparation method - Google Patents
Laminated solar cell based on different-grain-diameter PbS quantum dots and preparation method Download PDFInfo
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- CN103346176A CN103346176A CN2013102410580A CN201310241058A CN103346176A CN 103346176 A CN103346176 A CN 103346176A CN 2013102410580 A CN2013102410580 A CN 2013102410580A CN 201310241058 A CN201310241058 A CN 201310241058A CN 103346176 A CN103346176 A CN 103346176A
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Abstract
The invention discloses a laminated solar cell based on different-grain-diameter PbS quantum dots. The laminated solar cell is formed by an ITO glass layer, a TiO2 nanocrystalline layer, a small-grain-diameter PbS quantum dot thin film layer, an ITO layer, a TiO2 thin film layer, a large-grain-diameter PbS quantum dot thin film layer and a gold electrode in a laminated mode. A preparation method comprises the steps of coating a dry and clean ITO substrate in a spinning mode by TIO2 nanocrystalline, coating the dry and clean ITO substrate by small-grain-diameter PbS quantum dots in a spinning mode after the dry and clean ITO substrate is dried, sequentially conducting sputtering and magnetic control over the ITO thin film and the TiO2 thin film, then coating the dry and clean ITO substrate by large-grain-diameter PbS quantum dots in a spinning mode, and finally conducting vacuum evaporation on the gold electrode. The preparation method has the advantages that the two heterojunction solar cells based on the PbS quantum dots are laminated, the cell with the small-grain-diameter PbS quantum dots is arranged outside, the cell with the large-grain-diameter PbS quantum dots is arranged inside, the aim that sunlight with the short wavelength and the sunlight with the long wavelength can both be absorbed and utilized is achieved, the utilization rate of solar spectra can be greatly improved, and therefore the performance of the cells can be effectively improved.
Description
Technical field
The present invention relates to field of photovoltaic devices, be specifically related to a kind of lamination solar cell and preparation method based on different-grain diameter PbS quantum dot.
Background technology
Because the Energy distribution in the sunlight spectrum is wideer, existing any semi-conducting material all can only absorb the wherein energy photon higher than edge energy.The less photon of energy will be absorbed by the back electrode metal through battery in the sunlight, is transformed into heat energy; High-energy photon exceeds the excess energy of energy gap width, then release the dot matrix atom that battery material itself is passed in effect by the energy calorimetric of photo-generated carrier, makes material heating itself.These energy all can not be passed to load by photo-generated carrier, become effective electric energy.Therefore the theoretical transformation efficient of unijunction solar cell is generally lower.
Sunlight spectrum can be divided into continuous some parts, lamination solar cell can have best matched materials with bandwidth and these parts, outside in be superimposed together by energy gap order from big to small, allow the short light of wavelength by the battery utilization of the wide gap material of ragged edge, the long light of wavelength can transmission enters to allow the battery utilization of narrower gap material, this just might become luminous energy into electric energy to greatest extent, can improve performance and stability greatly.
Quantum dot (quantum dots, QDs) be the aggregate of a limited number of nanoscale atom and molecule, general particle size range is at 2-20nm, because its grain size and its exciton Bohr radius are suitable thereby have a quantum size effect, namely exist discontinuously the highlyest to be occupied molecular orbit and the minimum molecular orbital energy level that do not occupied, and its energy gap reduces with particle diameter and constantly broadens.So can regulate the band gap width of quantum dot by the particle diameter of control quantum dot when synthetic, use commaterial in the lamination solar cell thereby can be implemented in, avoided seeking the trouble of the different materials of energy level coupling.
The exciton Bohr radius of PbS is bigger, realizes quantum size effect easily, can make its absorption adjustable from the infrared band to the visible waveband by the size of controlling the PbS quantum point grain diameter when synthetic.Thereby can realize to see sunlight the absorption of infrared band.
Existing patent based on the PbS quantum dot cell, the quantum dot sensitized ZnO nanometer sheet of useful PbS, also useful MDMO-PPV coats and is used for the bulk heterojunction solar cell behind the PbS quantum dot, wide spectrum solar cell based on different quantum dot sizes is also arranged, but any battery device that all is based on unijunction, and this patent is based on the lamination quantum dot cell of two heterojunction, and more effectively separate electronic and hole are conducive to improve battery performance.
Summary of the invention
The objective of the invention is to utilize at present solar cell the light of visible part wave band in the solar spectrum, cause battery efficiency problem on the low side, a kind of lamination solar cell and preparation method based on different-grain diameter PbS quantum dot is provided, this quantum dot lamination solar cell, regulate band gap by the size of regulating quantum point grain diameter, and by band gap order from big to small quanta point material outside in is superimposed together, make the light of the quanta point material absorption visible part of outside broad-band gap, the quanta point material of the inside narrow band gap absorbs the sunlight of infrared part, thereby improve the absorption to solar spectrum greatly, be conducive to improve battery efficiency.
Technical scheme of the present invention:
A kind of lamination solar cell of the PbS quantum dot based on different-grain diameter is by glassy layer, ITO layer, TiO
2Nanometer crystal layer, band gap are PbS quantum dot thin layer, the ITO(tin indium oxide of 1.6ev) layer, TiO
2Thin layer, band gap are that PbS quantum dot thin layer and gold (Au) electrode of 1ev is formed by stacking successively, and wherein the thickness of ITO layer is the 50-100 nanometer, TiO
2The thickness of nanometer crystal layer is the 30-50 nanometer, and the thickness of two-layer PbS quantum dot film is 100-500 nanometer, TiO
2The thickness of thin layer is 40nm, and the thickness of Au electrode is the 100-200 nanometer.
A kind of preparation method of lamination solar cell of the PbS quantum dot based on different-grain diameter, step is as follows:
1) glass substrate that will deposit ITO is earlier by after liquid detergent, deionized water, acetone, isopropyl alcohol and the ethanol ultrasonic cleaning, and 80 ℃ were descended dry 30 minutes in vacuum drying chamber;
2) with being put on the sol evenning machine behind the dried ito glass substrate cool to room temperature, with the TiO for preparing
2Precursor liquid is spin coating 20s under 1500 rpms rotating speed, 400 ℃ of following preannealings 10 minutes, repeats this process 1 time, to reach needed thickness then.Then it was annealed 1 hour down at 400 ℃;
3) band gap of preparing 25mg/ml respectively is that the band gap of the PbS quantum dot hexane solution of 1.6ev and 25mg/ml is that the PbS quantum dot hexane solution of 1ev is as spin coating liquid;
4) be put on the sol evenning machine behind the ITO slice, thin piece cool to room temperature of annealing being finished, the PbS quantum dot hexane solution 5-6 that drips band gap thereon and be 1.6ev drips, stop 5-10 second, descend spin coatings respectively 6 seconds and 20 seconds for 2000 rpms in 700 rpms of the slow-speed of revolution and high rotating speed;
5) the ITO slice, thin piece of the PbS quantum dot film that is 1.6ev with the good band gap of above-mentioned spin coating places 80 ℃ of following dry 30min of vacuum drying chamber;
6) step 4 and step 5 are repeated to be no less than 3 times, up to reaching thickness 200 nanometers that need;
7) ITO slice, thin piece that top drying is good in the percent by volume of normal temperature, oxygen is 1% oxygen and argon gas gaseous mixture, vacuum degree is 10
-3Under the environment of Pa, the TiO of the ito thin film of magnetron sputtering one deck 50 nanometer thickness and one deck 40 nanometer thickness successively
2Film, the former speed were 0.25 dust/second, and latter's speed was 0.2 dust/second;
8) the ITO slice, thin piece that top sputter is finished is placed on the sol evenning machine, and the PbS quantum dot hexane solution 5-6 that drips band gap thereon and be 1ev drips, and stops 5-10 second, in the spin coatings 6 seconds and 20 seconds respectively down of 2000 rpms of 700 rpms of the slow-speed of revolution and high rotating speeds;
9) the ITO slice, thin piece of the PbS quantum dot film that is 1ev with the good band gap of above-mentioned spin coating places 80 ℃ of following dry 30min of vacuum drying chamber;
10) step 8 and step 9 are repeated to be no less than 3 times, up to reaching thickness 200 nanometers that need;
11) top spin coating being finished also dry good ITO slice, thin piece is 10 in vacuum degree
-4Evaporation thickness is the Au electrode of 100 nanometers-200 nanometer under the Pa, namely finishes and makes this PbS quantum dot lamination solar cell device based on the different-grain diameter size.
Described TiO
2The preparation method of precursor liquid, selecting butyl titanate for use is raw material, absolute ethyl alcohol is solvent, glacial acetic acid and acetylacetone,2,4-pentanedione are catalyst and stabilizer, preparation process is as follows: 10 milliliters of high-pure anhydrous ethanol with 53 milliliters of Butyl Phthalate are mixed, wiring solution-forming a, in addition with 0.5 milliliter acetic acid, 0.5 the deionized water of milliliter and 27 milliliters high-pure anhydrous ethanol mixing wiring solution-forming b, solution b is slowly splashed among the solution a, stir, drip 0.3 milliliter acetylacetone,2,4-pentanedione more inward, then 30 ℃ of following water-bath heating 6 hours, add the N-N dimethyl formamide at last, stirred again 30 minutes, leave standstill under the room temperature and got final product in 24 hours.
Principle of the present invention and foundation:
The exciton Bohr radius of PbS is bigger, realizes quantum size effect easily, can regulate and control its band gap width by the size of control PbS quantum point grain diameter when synthetic, thus make its ABSORPTION EDGE from infrared to as seen adjustable.By the PbS quantum dot outside in is superimposed together by energy gap order from big to small, allow the short light of wavelength by the PbS quantum dot cell utilization of the broad-band gap of ragged edge, the long light of wavelength can transmission enters to allow the PbS quantum dot cell utilization of narrower energy gap, this has just improved the utilance to solar spectrum greatly, thereby can effectively improve battery performance.
Advantage of the present invention is: the present invention is by stacking up two heterojunction solar batteries based on the PbS quantum dot, make based on the battery of small particle diameter (broad-band gap) PbS quantum dot outside, based on the battery of big particle diameter (narrow band gap) PbS quantum dot inside, can realize that like this light and the long light of wavelength that the solar spectrum medium wavelength is short all can be absorbed and used, the utilance to solar spectrum can be improved greatly, thereby the performance of battery can be effectively improved.
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Description of drawings
Fig. 1 is the structural representation of this lamination solar cell device.
Among the figure: 1. glassy layer 2.ITO layer 3.TiO
2Nano-crystalline thin rete 4. band gap are the PbS quantum dot thin layer 5.ITO layer 6..TiO of 1.6ev
2Thin layer 7. band gap are PbS quantum dot thin layer 8. gold medals (Au) electrode layer of 1ev
Fig. 2 is the level structure figure of this lamination solar cell device.
Embodiment
Embodiment:
A kind of lamination solar cell of the PbS quantum dot based on different-grain diameter, as shown in drawings, by glassy layer 1, ITO layer 2, TiO
2Nanometer crystal layer 3, band gap are PbS quantum dot thin layer 4, the ITO(tin indium oxide of 1.6ev) layer 5, TiO
2 Thin layer 6, band gap are that PbS quantum dot thin layer 7 and gold (Au) electrode 8 of 1ev is formed by stacking, and wherein the thickness of ITO layer is 100 nanometers, TiO
2The thickness of nanometer crystal layer is 50 nanometers, and the thickness of two-layer PbS quantum dot film is 200 nanometers, TiO
2Film thickness layer by layer is 40 nanometers, and the thickness of Au electrode is 100 nanometers.
A kind of lamination solar cell preparation process of the PbS quantum dot based on different-grain diameter is as follows:
1) glass substrate that will deposit ITO is earlier by after liquid detergent, deionized water, acetone, isopropyl alcohol and the ethanol ultrasonic cleaning, and 80 ℃ were descended dry 30 minutes in vacuum drying chamber;
2) with being put on the sol evenning machine behind the dried ito glass substrate cool to room temperature, with the TiO for preparing
2Precursor liquid is spin coating 20s under 1500 rpms rotating speed, 400 ℃ of following preannealings 10 minutes, repeats this process 1 time then, to reach needed thickness, then with it 400 ℃ of annealing 1 hour down;
Described TiO
2The preparation method of precursor liquid, selecting butyl titanate for use is raw material, and absolute ethyl alcohol is solvent, and glacial acetic acid and acetylacetone,2,4-pentanedione are catalyst and stabilizer, and preparation process is as follows:
10 milliliters of high-pure anhydrous ethanol with 53 milliliters of Butyl Phthalate are mixed, wiring solution-forming a, in addition with 0.5 milliliter acetic acid, 0.5 milliliter deionized water and 27 milliliters high-pure anhydrous ethanol mixing wiring solution-forming b, solution b is slowly splashed among the solution a, stir, drip 0.3 milliliter acetylacetone,2,4-pentanedione more inward, then 30 ℃ of following water-bath heating 6 hours, add the N-N dimethyl formamide at last, stirred again 30 minutes, leave standstill under the room temperature and got final product in 24 hours;
3) band gap of preparing 25mg/ml respectively is that the band gap of the PbS quantum dot hexane solution of 1.6ev and 25mg/ml is that the PbS quantum dot hexane solution of 1ev is as spin coating liquid;
4) be put on the sol evenning machine behind the ITO cool to room temperature after will annealing, the PbS quantum dot hexane solution 5-6 that drips band gap thereon and be 1.6ev drips, stop 5-10 second, descend spin coatings respectively 6 seconds and 20 seconds for 2000 rpms in 700 rpms of the slow-speed of revolution and high rotating speed;
5) the ITO slice, thin piece of the PbS quantum dot film that is 1.6ev with the good band gap of above-mentioned spin coating places 80 ℃ of following dry 30min of vacuum drying chamber;
6) step 4 and step 5 are repeated 4 times, make to reach thickness 200 nanometers that need;
7) top drying is good ITO slice, thin piece is at normal temperature, and the percent by volume of oxygen is in 1% the oxygen and argon gas gaseous mixture, vacuum degree is 10
-3Under the environment of Pa, the TiO of the ito thin film of magnetron sputtering one deck 50 nanometer thickness and one deck 40 nanometer thickness successively
2Film, the former speed were 0.25 dust/second, and latter's speed was 0.2 dust/second;
8) the ITO slice, thin piece that top sputter is finished is placed on the sol evenning machine, and the PbS quantum dot hexane solution 5-6 that drips band gap thereon and be 1ev drips, and stops 5-10 second, in the spin coatings 6 seconds and 20 seconds respectively down of 2000 rpms of 700 rpms of the slow-speed of revolution and high rotating speeds;
9) the ITO slice, thin piece of the PbS quantum dot film that is 1ev with the good band gap of above-mentioned spin coating places 80 ℃ of following dry 30min of vacuum drying chamber;
10) step 9 and step 10 are repeated 4 times, make to reach thickness 200 nanometers that need;
11) top spin coating being finished also dry good ITO slice, thin piece is 10 in vacuum degree
-4Evaporation thickness is the metal A u electrode of 100 nanometers under the Pa, namely finishes and makes this PbS quantum dot lamination solar cell device based on the different-grain diameter size.
Fig. 2 is the level structure figure of this lamination solar cell device, show among the figure: it is the light induced electron of the PbS quantum dot generation of 1.6ev that the ITO end is collected by band gap, it is the photohole that the PbS quantum dot of 1ev produces that the Au electrode is collected band gap, and the light induced electron that the PbS quantum dot that the band gap photohole that to be the PbS quantum dot of 1.6ev produce and band gap are 1ev produces is compound in one deck ITO of middle sputter.
Claims (3)
1. the lamination solar cell based on the PbS quantum dot of different-grain diameter is characterized in that: by glassy layer, ITO layer, TiO
2Nanometer crystal layer, band gap are PbS quantum dot thin layer, ITO layer, the TiO of 1.6ev
2Thin layer, band gap are that PbS quantum dot thin layer and the gold electrode of 1ev is formed by stacking, and wherein the thickness of ITO layer is the 50-100 nanometer, TiO
2The thickness of nanometer crystal layer is the 30-50 nanometer, and the thickness of two-layer PbS quantum dot film is 100-500 nanometer, TiO
2Film thickness layer by layer is 40nm, and the thickness of Au electrode is the 100-200 nanometer.
2. one kind according to claim 1 based on the preparation method of the lamination solar cell of the PbS quantum dot of different-grain diameter, it is characterized in that step is as follows:
1) glass substrate that will deposit ITO is earlier by after liquid detergent, deionized water, acetone, isopropyl alcohol and the ethanol ultrasonic cleaning, and 80 ℃ were descended dry 30 minutes in vacuum drying chamber;
2) with being put on the sol evenning machine behind the dried ito glass substrate cool to room temperature, with the TiO for preparing
2Precursor liquid is spin coating 20s under 1500 rpms rotating speed, 400 ℃ of following preannealings 10 minutes, repeats this process 1 time then, to reach needed thickness, then with it 400 ℃ of annealing 1 hour down;
3) band gap of preparing 25mg/ml respectively is that the band gap of the PbS quantum dot hexane solution of 1.6ev and 25mg/ml is that the PbS quantum dot hexane solution of 1ev is as spin coating liquid;
4) be put on the sol evenning machine behind the ITO slice, thin piece cool to room temperature of annealing being finished, the PbS quantum dot hexane solution 5-6 that drips band gap thereon and be 1.6ev drips, stop 5-10 second, descend spin coatings respectively 6 seconds and 20 seconds for 2000 rpms in 700 rpms of the slow-speed of revolution and high rotating speed;
5) the ITO slice, thin piece of the PbS quantum dot film that is 1.6ev with the good band gap of above-mentioned spin coating places 80 ℃ of following dry 30min of vacuum drying chamber;
6) step 4 and step 5 are repeated to be no less than 3 times, up to reaching thickness 200 nanometers that need;
7) ITO slice, thin piece that top drying is good in the percent by volume of normal temperature, oxygen is 1% oxygen and argon gas gaseous mixture, vacuum degree is 10
-3Under the environment of Pa, the TiO of the ito thin film of magnetron sputtering one deck 50 nanometer thickness and one deck 40 nanometer thickness successively
2Film, the former speed were 0.25 dust/second, and latter's speed was 0.2 dust/second;
8) the ITO slice, thin piece that top sputter is finished is placed on the sol evenning machine, and the PbS quantum dot hexane solution 5-6 that drips band gap thereon and be 1ev drips, and stops 5-10 second, in the spin coatings 6 seconds and 20 seconds respectively down of 2000 rpms of 700 rpms of the slow-speed of revolution and high rotating speeds;
9) the ITO slice, thin piece of the PbS quantum dot film that is 1ev with the good band gap of above-mentioned spin coating places 80 ℃ of following dry 30min of vacuum drying chamber;
10) step 8 and step 9 are repeated to be no less than 3 times, up to reaching thickness 200 nanometers that need;
11) top spin coating being finished also dry good ITO slice, thin piece is 10 in vacuum degree
-4Evaporation thickness is the Au electrode of 100-200 nanometer under the Pa, namely finishes and makes this PbS quantum dot lamination solar cell device based on the different-grain diameter size.
3. according to the preparation method of the lamination solar cell of the described PbS quantum dot based on different-grain diameter of claim 2, it is characterized in that: described TiO
2The preparation method of precursor liquid, selecting butyl titanate for use is raw material, and absolute ethyl alcohol is solvent, and glacial acetic acid and acetylacetone,2,4-pentanedione are catalyst and stabilizer, and preparation process is as follows:
10 milliliters of high-pure anhydrous ethanol with 53 milliliters of Butyl Phthalate are mixed, wiring solution-forming a, in addition with 0.5 milliliter acetic acid, 0.5 milliliter deionized water and 27 milliliters high-pure anhydrous ethanol mixing wiring solution-forming b, solution b is slowly splashed among the solution a, stir, drip 0.3 milliliter acetylacetone,2,4-pentanedione more inward, then 30 ℃ of following water-bath heating 6 hours, add the N-N dimethyl formamide at last, stirred again 30 minutes, left standstill under the room temperature 24 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070843A (en) * | 2015-08-14 | 2015-11-18 | 陕西师范大学 | Perovskite solar energy battery and preparation method |
| CN105161562A (en) * | 2015-09-15 | 2015-12-16 | 华南理工大学 | PbS quantum dot heterojunction solar cell employing solvent regulation and control and preparation method of PbS quantum-dot heterojunction solar cell |
| CN105679858A (en) * | 2016-01-20 | 2016-06-15 | 苏州大学 | Nanocrystalline composite center-based stacked solar cell and preparation method thereof |
| CN111477644A (en) * | 2020-03-31 | 2020-07-31 | 东南大学 | Near-infrared/visible light/ultraviolet integrated spectral imaging device and imaging method |
| CN114249296A (en) * | 2021-12-18 | 2022-03-29 | 河北工业大学 | Hetero-semiconductor nano-particle and method for preparing triboelectrification film |
| CN116130531A (en) * | 2022-09-07 | 2023-05-16 | 德州学院 | Quantum dot laminated solar cell and preparation method thereof |
| CN114823149B (en) * | 2022-05-13 | 2024-04-26 | 电子科技大学长三角研究院(湖州) | Au nanoparticle composite environment-friendly quantum dot sensitized solar electrode and preparation method and application thereof |
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| CN105070843A (en) * | 2015-08-14 | 2015-11-18 | 陕西师范大学 | Perovskite solar energy battery and preparation method |
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| CN105161562B (en) * | 2015-09-15 | 2017-04-19 | 华南理工大学 | PbS quantum dot heterojunction solar cell employing solvent regulation and control and preparation method of PbS quantum-dot heterojunction solar cell |
| CN105679858A (en) * | 2016-01-20 | 2016-06-15 | 苏州大学 | Nanocrystalline composite center-based stacked solar cell and preparation method thereof |
| CN111477644A (en) * | 2020-03-31 | 2020-07-31 | 东南大学 | Near-infrared/visible light/ultraviolet integrated spectral imaging device and imaging method |
| CN111477644B (en) * | 2020-03-31 | 2023-04-18 | 东南大学 | Near-infrared/visible light/ultraviolet integrated spectral imaging device and imaging method |
| CN114249296A (en) * | 2021-12-18 | 2022-03-29 | 河北工业大学 | Hetero-semiconductor nano-particle and method for preparing triboelectrification film |
| CN114823149B (en) * | 2022-05-13 | 2024-04-26 | 电子科技大学长三角研究院(湖州) | Au nanoparticle composite environment-friendly quantum dot sensitized solar electrode and preparation method and application thereof |
| CN116130531A (en) * | 2022-09-07 | 2023-05-16 | 德州学院 | Quantum dot laminated solar cell and preparation method thereof |
| WO2024050927A1 (en) * | 2022-09-07 | 2024-03-14 | 德州学院 | Quantum dot laminated solar cell and manufacturing method therefor |
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Application publication date: 20131009 |